EP2032589A1 - Solvent system for the preparation of n-alkyl thiophosphoric triamide solutions, composition containing n-alkyl thiophosphoric triamide and the use thereof - Google Patents

Solvent system for the preparation of n-alkyl thiophosphoric triamide solutions, composition containing n-alkyl thiophosphoric triamide and the use thereof

Info

Publication number
EP2032589A1
EP2032589A1 EP07721836A EP07721836A EP2032589A1 EP 2032589 A1 EP2032589 A1 EP 2032589A1 EP 07721836 A EP07721836 A EP 07721836A EP 07721836 A EP07721836 A EP 07721836A EP 2032589 A1 EP2032589 A1 EP 2032589A1
Authority
EP
European Patent Office
Prior art keywords
thiophosphoric triamide
alkyl
solvent system
sub
solutions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP07721836A
Other languages
German (de)
French (fr)
Other versions
EP2032589B1 (en
Inventor
Petr Cigler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agra Group AS
Original Assignee
Agra Group AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=38548488&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2032589(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Agra Group AS filed Critical Agra Group AS
Priority to PL07721836T priority Critical patent/PL2032589T3/en
Publication of EP2032589A1 publication Critical patent/EP2032589A1/en
Application granted granted Critical
Publication of EP2032589B1 publication Critical patent/EP2032589B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/224—Phosphorus triamides

Definitions

  • the invention relates to the composition of novel solvent systems for the urease inhibitors based on N-alkyl thiophosphoric triamides, the compositions containing N- alkyl thiophosphoric triamide and the use of these compositions.
  • Urea constitutes 46 % of the worldwide consumption of nitrogen in agriculture and is the most widely used nitrogen fertilizer. However, after its application to soil, its partial hydrolysis to yield ammonia and carbon dioxide occurs. This process is catalysed by the enzyme urease, which is produced by some bacteria and fungi. The gaseous products formed by the hydrolysis reaction (ammonia and carbon dioxide) volatilize to the atmosphere and thus, substantial losses from the total amount of the nitrogen applied to the field occur.
  • urease inhibitors that are applied together with urea.
  • urease inhibitors include the thiophosphoric triamide compounds disclosed in the US Pat. No. 4,530,714, above all N-(n-butyl)thiophosphoric triamide (NBPT).
  • NBPT N-(n-butyl)thiophosphoric triamide
  • NBPT N-(n-butyl)thiophosphoric triamide
  • N-(n-butyl)thiophosphoric triamide (NBPT) and aliphatic diols and triols or their esters are described, containing up to 50 wt. % of NBPT, preferably 20 - 30 wt. % NBPT.
  • NBPT N-(n-butyl)thiophosphoric triamide
  • aliphatic diols and triols or their esters are described, containing up to 50 wt. % of NBPT, preferably 20 - 30 wt. % NBPT.
  • These mixtures are suitable for the impregnation of granular urea, but they are liquid only at the temperatures above 15 0 C. Below this temperature, they solidify or crystallize. This undesired property renders the manipulation with the solutions and their application to granular urea in the course of its production, particularly during the cold periods of the year, when the temperature can fall deep below 0 0 C.
  • Object of the present invention is a solvent system for the preparation of N-alkyl thiophosphoric triamide solutions, containing one or more glycol ethers of the general formula I
  • R 1 is hydrogen or methyl
  • the alkyl group of N-alkyl triphosphoric triamides is selected from the group comprising linear or branched alkyl chains having 1 to 8 carbon atoms and cycloalkyl chains having 3 to 8 carbon atoms.
  • glycol ethers of the general formula I preferably diethyleneglycol monomethylether, dipropyleneglycol monomethylether, triethyleneglycol monomethylether and diethyleneglycol monobutylether can be used.
  • the most preferred solvent is diethyleneglycol monomethylether.
  • the auxiliary substances improving the stability and applicability properties of the solutions can be crystallization inhibitors, surface active agents or colouring agents.
  • polyvinylpyrrolidone or N-methylpyrrolidone can be used as the crystallization inhibitors.
  • polyvinylpyrrolidone in the concentration range of from 0.01 to 5 wt. % is used as the crystallization inhibitor.
  • This compound in non-toxic and is used in similar concentrations e.g. in medicine as the additive to eye-drops.
  • Object of the present invention is further a composition containing N-alkyl thiophosphoric triamide, which contains at least one N-alkyl thiophosphoric triamide and the solvent system of the present invention.
  • the N-alkyl thiophosphoric triamide is N-(n-butyl) thiophosphoric triamide.
  • the composition of the present invention contains 1 to 50 wt. % of N-(n- butyl) thiophosphoric triamide.
  • composition of the present invention contains 10 to 40 wt. % of N-(n-butyl) thiophosphoric triamide.
  • the composition of the present invention contains 20 to 30 wt. % of N-(n-butyl) thiophosphoric triamide.
  • a further object of the present invention is the use of the composition containing N- alkyl thiophosphoric triamide as an urease inhibitor in urea-containing fertilizers.
  • the urea-containing fertilizers can be solid, then the composition of the present invention can be added into the mixture for the manufacture of these fertilizers, or the fertilizer particles, e.g. granules, can be impregnated by the composition of the invention.
  • the urea-containing fertilizer can be liquid, then the composition of the present invention can be admixed to the liquid fertilizer.
  • the solvent systems of the present invention show properties, which are advantageous for the application in agriculture: a high concentration of N-(n-butyl) thiophosphoric triamide (NBPT) in the solution can be achieved in these solvent systems, and NBPT is stabilized in these solutions by the solvent systems of the invention.
  • NBPT N-(n-butyl) thiophosphoric triamide
  • the solvent systems of the present invention show a high resistance against solidifying and crystallization in comparison with the solvent systems known in the art, even at very low temperatures (-20 0 C). They are miscible with water, not toxic, show a very low volatility and flammability. Thanks to their solvent and chemical properties, the solvent systems of the invention are suitable for impregnation of granular urea. A further advantage is that the commercially available technical grade components of the solvent systems of the invention contain a minimum amount of water - in the order of hundredth of percent - and they are available at low cost.
  • N-(n-butyl) thiophosphoric triamide (NBPT) in the solvent systems of the present invention have, in contrast to the solvent systems known in the art, the capability to remain liquid at very low temperatures. This capability is due to the chemical nature of the solvents and can be further improved by the presence of polyvinylpyrrolidone in the solution as the crystallization inhibitor.
  • NBPT N-(n-butyl) thiophosphoric triamide
  • the concentration of technical-grade NBPT in the solutions was 25 wt. %.
  • the temperature -20 0 C was selected, which allowed for direct assessment of the behavior of the solutions under the storage conditions corresponding to the temperature regime of the cold months of the year.
  • the solutions were examined after four months of storage. The results are summarized in Table 1.
  • the flowability was assessed visually as the following grades: excellent, good, bad. Further, the presence of NBPT crystals in the solution was examined (yes-no). In case of the presence of the crystals in the solution, the flowability was not assessed.
  • glycol ethers were selected for testing: dipropyleneglycol monomethylether (MDPG) diethyleneglycol monomethylether (MDGE) triethyleneglycol monomethylether (MTGE) diethyleneglycol monobutylether (BDGE)
  • MDPG dipropyleneglycol monomethylether
  • MDGE diethyleneglycol monomethylether
  • MTGE triethyleneglycol monomethylether
  • BDGE diethyleneglycol monobutylether
  • Polyvinylpyrrolidone (PVP) and N-methyl pyrrolidone (NMP) were used as the crystallization inhibitors.
  • PVP polyvinylpyrrolidone
  • NMP N-methyl pyrrolidone
  • results for MDPG show the positive effect of polyvinylpyrrolidone, which at the concentration of 1 wt. % completely inhibits the crystallization.
  • a suitable solvent is also MTGE, in which NBPT does not crystallize at -20 0 C at the concentration of polyvinylpyrrolidone being 0.1 wt. %.
  • Table 1 Effect of the composition of the solvent systems on the flowability and on the crystallization of NBPT from its solutions at the temperature of -20 0 C.
  • the concentration of technical-grade NBPT in the solutions was 25 wt. %.
  • the solutions were examined after four months of storage. The results are summarized in Table 2.
  • the flowability was assessed visually as the following grades: excellent, good, bad. Further, the presence of NBPT crystals in the solution was examined (yes-no). In case of the presence of the crystals in the solution, the flowability was not assessed.
  • glycol ethers were selected for testing: dipropyleneglycol monomethylether (MDPG) diethyleneglycol monomethylether (MDGE) triethyleneglycol monomethylether (MTGE) diethyleneglycol monobutylether (BDGE)
  • MDPG dipropyleneglycol monomethylether
  • MDGE diethyleneglycol monomethylether
  • MTGE triethyleneglycol monomethylether
  • BDGE diethyleneglycol monobutylether
  • Polyvinylpyrrolidone (PVP) and N-methyl pyrrolidone (NMP) were used as the crystallization inhibitors.
  • PVP polyvinylpyrrolidone
  • NMP N-methyl pyrrolidone
  • N-(n-butyl) thiophosphoric triamide (NBPT) A high stability of N-(n-butyl) thiophosphoric triamide (NBPT) in the solvent system is the key issue for the long-term storage of its solutions. During a longer storage period, the presence of water causes the decomposition of N-(n-butyl)thiophosphoric triamide (NBPT) into non-effective substances and is the main cause of the NBPT degradation during the long-term storage.
  • the solvent systems of the present invention show a stabilizing effect towards NBPT.
  • All glycol ethers used in this example are commercially available in very good quality (the content of water does not exceed the concentration of 0.05 wt. %). Nevertheless, to confirm the stabilization effect of the solvents, the content of water was artificially increased to 1 wt. %.
  • the thus adjusted solvent systems simulate the effect of the moisture on NBPT (higher contents of the moisture than 1 wt. % are uncommon).
  • glycol ethers containing 1 wt. % of water For the verification of the long-term stability of NBPT solutions in glycol ethers containing 1 wt. % of water, the following glycol ethers were selected: dipropyleneglycol monomethylether (MDPG) diethyleneglycol monomethylether (MDGE) triethyleneglycol monomethylether (MTGE)
  • MDPG dipropyleneglycol monomethylether
  • MDGE diethyleneglycol monomethylether
  • MTGE triethyleneglycol monomethylether
  • the determination of the content of NBPT in individual terms was carried out by reverse-phase HPLC with UV detection in the mobile phase containing 25 vol. % acetonitrile and 75 vol. % 0.005M ammonium acetate.
  • the chromatogram was evaluated at the wavelength of 193 nm.
  • the mobile phase flow was 1 ml/min, the column temperature was 40 0 C.
  • the injected volume was 5 ⁇ l.
  • the evaluation was carried out by the method of external standard with the calibration using a calibration line. The results are summarized in Tab. 3.
  • solutions of N-alkyl thiophosphoric acid triamides in the solvent systems of the present invention can be long-term stored, used for the impregnation of solid urea- containing fertilizers, such as e.g. granular urea, added into the mixture for the manufacture of solid urea-containing fertilizers or added into liquid urea-containing fertilizers.
  • solid urea- containing fertilizers such as e.g. granular urea

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Fertilizers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Object of the present invention are novel solvent systems for the preparation of N-alkyl thiophosphoric triamide solutions, containing one or more glycol ethers of the general formula (I), wherein R<SUP>1</SUP> is hydrogen or methyl, R<SUP>2</SUP> is selected from the group consisting of C<SUB>1</SUB>-C<SUB>6</SUB> alkyl, C<SUB>3</SUB>-C<SUB>6</SUB> isoalkyl, C<SUB>4</SUB>-C<SUB>6</SUB> tertiary alkyl, n = 2-4, and optionally further auxiliary substances improving the stability and applicability properties of the solutions. Object of the invention are further compositions containing N-alkyl thiophosphoric triamide, containing at least one N-alkyl thiophosphoric triamide and the solvent system of the invention, and also the use of the composition containing N-alkyl thiophosphoric triamide.

Description

Solvent system for the preparation of N-alkyl thiophosphoric triamide solutions, composition containing N-alkyl thiophosphoric triamide and the use thereof
Technical Field
The invention relates to the composition of novel solvent systems for the urease inhibitors based on N-alkyl thiophosphoric triamides, the compositions containing N- alkyl thiophosphoric triamide and the use of these compositions.
Background Art
Urea constitutes 46 % of the worldwide consumption of nitrogen in agriculture and is the most widely used nitrogen fertilizer. However, after its application to soil, its partial hydrolysis to yield ammonia and carbon dioxide occurs. This process is catalysed by the enzyme urease, which is produced by some bacteria and fungi. The gaseous products formed by the hydrolysis reaction (ammonia and carbon dioxide) volatilize to the atmosphere and thus, substantial losses from the total amount of the nitrogen applied to the field occur.
The hydrolysis process can be considerably decelerated by urease inhibitors that are applied together with urea. Among the most effective urease inhibitors are the thiophosphoric triamide compounds disclosed in the US Pat. No. 4,530,714, above all N-(n-butyl)thiophosphoric triamide (NBPT). The use of NBPT was experimentally verified and this compound is now industrially available for the use in agriculture (Watson, CJ. (2005) Proc. Internat. Fertiliser Soc. 454, 1-38).
Industrial grade N-(n-butyl)thiophosphoric triamide (NBPT) is a solid, waxy compound, which decomposes by the action of moisture and elevated temperature. With regard to its consistence, its direct application onto urea particles is very difficult. Technologically more advantageous is the use of the NBPT solutions in a suitable solvent, which should comply with some basic requirements: high solubility and stability of NBPT in the solvent, resistance of the NBPT solutions against the crystallization at a low temperature, low viscosity of the concentrated solutions of NBPT, low toxicity, volatility and flammability, minimum content of water in the commercially available form of the solvent, low cost. In the US Pat. No. 5,698,003, mixtures of N-(n-butyl)thiophosphoric triamide (NBPT) and aliphatic diols and triols or their esters are described, containing up to 50 wt. % of NBPT, preferably 20 - 30 wt. % NBPT. These mixtures are suitable for the impregnation of granular urea, but they are liquid only at the temperatures above 15 0C. Below this temperature, they solidify or crystallize. This undesired property renders the manipulation with the solutions and their application to granular urea in the course of its production, particularly during the cold periods of the year, when the temperature can fall deep below 0 0C. US 5,698,003 teaches that the addition of the so-called Jiquid amides"(e.g. 10 wt. % of N-methylpyrrolidone) to these solvent can shift the solidification temperature to 0 0C. The liquid amides, however, are health- deleterious (N-methylpyrrolidone is often classified among carcinogenic and teratogenic compounds) and the solidifying temperature achieved is still not sufficient for the manipulation at low temperatures or at freezing.
Another issue is the technical quality and hygroscopicity of the commercially available diols and triols. They often contain few tenths of percent of water and this amount can further increase during storage due to the hygroscopicity of the solvents. During a longer storage period, the presence of water causes the decomposition of N-(n-butyl) thiophosphoric triamide (NBPT) into non-effective substances and is the main cause of the NBPT degradation during a long-term storage. The instability of NBPT towards hydrolysis is well known, e.g. because of it, NBPT is poorly utilizable on moist soils.
The above mentioned disadvantages can be solved by the solvent systems according to the present invention.
Disclosure of the Invention
Object of the present invention is a solvent system for the preparation of N-alkyl thiophosphoric triamide solutions, containing one or more glycol ethers of the general formula I
(I) wherein R1 is hydrogen or methyl, R2 is selected from the group consisting of C1-C6 alkyl, C3-C6 isoalkyl, C4-C6 tertiary alkyl, n = 2-4, and optionally further auxiliary substances improving the stability and applicability properties of the solutions.
The alkyl group of N-alkyl triphosphoric triamides is selected from the group comprising linear or branched alkyl chains having 1 to 8 carbon atoms and cycloalkyl chains having 3 to 8 carbon atoms.
From the group of glycol ethers of the general formula I, preferably diethyleneglycol monomethylether, dipropyleneglycol monomethylether, triethyleneglycol monomethylether and diethyleneglycol monobutylether can be used. The most preferred solvent is diethyleneglycol monomethylether.
The auxiliary substances improving the stability and applicability properties of the solutions can be crystallization inhibitors, surface active agents or colouring agents.
In a preferred embodiment, polyvinylpyrrolidone or N-methylpyrrolidone can be used as the crystallization inhibitors.
Preferably, polyvinylpyrrolidone in the concentration range of from 0.01 to 5 wt. % is used as the crystallization inhibitor. This compound in non-toxic and is used in similar concentrations e.g. in medicine as the additive to eye-drops.
For the indication of homogeneity of the coating of a solid urea-containing fertilizer (e.g. granular urea) by the solution of N-alkyl thiophosphoric triamide, common agricultural or food colouring agents can be added into the solvent system.
For achieving a sufficient coating of the surface of a solid urea-containing fertilizer (e.g. granular urea) by the solution of N-alkyl thiophosphoric triamide, surface active agents commonly used in agriculture can be added into the solvent system.
Object of the present invention is further a composition containing N-alkyl thiophosphoric triamide, which contains at least one N-alkyl thiophosphoric triamide and the solvent system of the present invention. In a preferred embodiment, the N-alkyl thiophosphoric triamide is N-(n-butyl) thiophosphoric triamide.
Preferably, the composition of the present invention contains 1 to 50 wt. % of N-(n- butyl) thiophosphoric triamide.
More preferably, the composition of the present invention contains 10 to 40 wt. % of N-(n-butyl) thiophosphoric triamide.
Most preferably, the composition of the present invention contains 20 to 30 wt. % of N-(n-butyl) thiophosphoric triamide.
A further object of the present invention is the use of the composition containing N- alkyl thiophosphoric triamide as an urease inhibitor in urea-containing fertilizers. The urea-containing fertilizers can be solid, then the composition of the present invention can be added into the mixture for the manufacture of these fertilizers, or the fertilizer particles, e.g. granules, can be impregnated by the composition of the invention. In another embodiment of the invention, the urea-containing fertilizer can be liquid, then the composition of the present invention can be admixed to the liquid fertilizer.
The solvent systems of the present invention show properties, which are advantageous for the application in agriculture: a high concentration of N-(n-butyl) thiophosphoric triamide (NBPT) in the solution can be achieved in these solvent systems, and NBPT is stabilized in these solutions by the solvent systems of the invention.
The solvent systems of the present invention show a high resistance against solidifying and crystallization in comparison with the solvent systems known in the art, even at very low temperatures (-20 0C). They are miscible with water, not toxic, show a very low volatility and flammability. Thanks to their solvent and chemical properties, the solvent systems of the invention are suitable for impregnation of granular urea. A further advantage is that the commercially available technical grade components of the solvent systems of the invention contain a minimum amount of water - in the order of hundredth of percent - and they are available at low cost.
The invention is further illustrated by the following examples, which should not be construed as further limiting. Examples
Example 1
The solutions of N-(n-butyl) thiophosphoric triamide (NBPT) in the solvent systems of the present invention have, in contrast to the solvent systems known in the art, the capability to remain liquid at very low temperatures. This capability is due to the chemical nature of the solvents and can be further improved by the presence of polyvinylpyrrolidone in the solution as the crystallization inhibitor. In this example, the improvement of the flowability of the concentrated solutions of NBPT and lowering the crystallization point of NBPT with the use of the solvent system of the present invention in comparison with the systems known in the art is shown.
The concentration of technical-grade NBPT in the solutions was 25 wt. %. For testing, the temperature -20 0C was selected, which allowed for direct assessment of the behavior of the solutions under the storage conditions corresponding to the temperature regime of the cold months of the year. The solutions were examined after four months of storage. The results are summarized in Table 1. The flowability was assessed visually as the following grades: excellent, good, bad. Further, the presence of NBPT crystals in the solution was examined (yes-no). In case of the presence of the crystals in the solution, the flowability was not assessed.
The following glycol ethers were selected for testing: dipropyleneglycol monomethylether (MDPG) diethyleneglycol monomethylether (MDGE) triethyleneglycol monomethylether (MTGE) diethyleneglycol monobutylether (BDGE)
Polyvinylpyrrolidone (PVP) and N-methyl pyrrolidone (NMP) were used as the crystallization inhibitors. For comparison with the state of art, the mixture containing propylene glycol (PG) as the solvent and 10 wt. % of N-methyl pyrrolidone (NMP) described in the US Pat. No. 5,698,003 was used.
The results show that MDGE is the optimal solvent for NBPT with regard to the stability of the solution at low temperatures. The crystallization of NBPT from the solution does not occur at -20 0C. The presence of the crystallization inhibitor is not necessary for maintaining NBPT in this solution, nevertheless, its use does not adversely affect the flowability of the solution.
The results for MDPG show the positive effect of polyvinylpyrrolidone, which at the concentration of 1 wt. % completely inhibits the crystallization.
A suitable solvent is also MTGE, in which NBPT does not crystallize at -20 0C at the concentration of polyvinylpyrrolidone being 0.1 wt. %.
Table 1: Effect of the composition of the solvent systems on the flowability and on the crystallization of NBPT from its solutions at the temperature of -20 0C.
Concentration
MDPG of the MDGE MTGE BDGE PG
Crystallization crystallization - inhibitor inhibitor flowability crystallization flowability crystallization flowability crystallization flowability crystallization flowability crystallization
[Wt. %]
— — — yes excellent no — yes — yes — yes
PVP 0.1 — yes excellent no good no N/A N/A N/A N/A
PVP 0.25 — yes excellent no good no N/A N/A N/A N/A
PVP 0.5 — yes excellent no good no N/A N/A N/A N/A
PVP 0.75 — yes excellent no bad no N/A N/A N/A N/A
PVP 1 good no excellent no bad no N/A N/A N/A N/A
NMP 10 excellent no excellent no good no N/A N/A — yes
N/A - not determined
Example 2
In this example, the improvement of the flowability of the concentrated solutions of N- (n-butyl) triphosphoric triamide (NBPT) and the lowering of the crystallization point of NBPT with the use of the solvent system of the present invention at -5 0C is described.
The concentration of technical-grade NBPT in the solutions was 25 wt. %. The solutions were examined after four months of storage. The results are summarized in Table 2. The flowability was assessed visually as the following grades: excellent, good, bad. Further, the presence of NBPT crystals in the solution was examined (yes-no). In case of the presence of the crystals in the solution, the flowability was not assessed.
The following glycol ethers were selected for testing: dipropyleneglycol monomethylether (MDPG) diethyleneglycol monomethylether (MDGE) triethyleneglycol monomethylether (MTGE) diethyleneglycol monobutylether (BDGE)
Polyvinylpyrrolidone (PVP) and N-methyl pyrrolidone (NMP) were used as the crystallization inhibitors. For comparison with the state of art, the mixture containing propylene glycol (PG) as the solvent and 10 wt. % of N-methyl pyrrolidone (NMP) described in the US Pat. No. 5,698,003 was used.
The results are almost identical to the results obtained for the temperature of -20 0C (Example 1), only in the case of MDPG, polyvinylpyrrolidone inhibits the crystallization already at the concentration of 0.75 wt. %, and in the case of BDGE, the crystallization does not occur at the temperature of -5 0C, whereas the flowability of the solution is excellent. Table 2: Effect of the composition of the solvent systems on the flowability and on the crystallization of NBPT from its solutions at the temperature of -5 0C.
Concentration
MDPG of the MDGE MTGE BDGE PG
Crystallization crystallizaϋon - inhibitor inhibitor flowability crystallization flowability crystallization flowability crystallization flowability crystallization flowability crystallization
[Wt. %]
— — — yes excellent no — yes excellent no — yes
PVP 0,1 — yes excellent no good no N/A N/A N/A N/A
PVP 0,25 — yes excellent no good no N/A N/A N/A N/A
PVP 0,5 — yes excellent no good no N/A N/A N/A N/A
PVP 0,75 good no excellent no bad no N/A N/A N/A N/A
PVP 1 good no excellent no bad no N/A N/A N/A N/A
NMP 10 excellent no excellent no good no N/A N/A — yes
N/A - not determined
Example 3
Stability of the solutions in time
A high stability of N-(n-butyl) thiophosphoric triamide (NBPT) in the solvent system is the key issue for the long-term storage of its solutions. During a longer storage period, the presence of water causes the decomposition of N-(n-butyl)thiophosphoric triamide (NBPT) into non-effective substances and is the main cause of the NBPT degradation during the long-term storage.
The solvent systems of the present invention show a stabilizing effect towards NBPT. All glycol ethers used in this example are commercially available in very good quality (the content of water does not exceed the concentration of 0.05 wt. %). Nevertheless, to confirm the stabilization effect of the solvents, the content of water was artificially increased to 1 wt. %. The thus adjusted solvent systems simulate the effect of the moisture on NBPT (higher contents of the moisture than 1 wt. % are uncommon).
For the verification of the long-term stability of NBPT solutions in glycol ethers containing 1 wt. % of water, the following glycol ethers were selected: dipropyleneglycol monomethylether (MDPG) diethyleneglycol monomethylether (MDGE) triethyleneglycol monomethylether (MTGE)
The solutions of NBPT in these solvents having the concentration ca 20 wt. % (weighed portion) were stored at room temperature at daylight in glass, well-sealed vials.
The determination of the content of NBPT in individual terms was carried out by reverse-phase HPLC with UV detection in the mobile phase containing 25 vol. % acetonitrile and 75 vol. % 0.005M ammonium acetate. The chromatogram was evaluated at the wavelength of 193 nm. The mobile phase flow was 1 ml/min, the column temperature was 40 0C. The injected volume was 5 μl. The evaluation was carried out by the method of external standard with the calibration using a calibration line. The results are summarized in Tab. 3.
Table 3: Summary of the results (in wt. %) of the determination of the NBPT content in the time t = 0 (immediately after the preparation of the solution), in the time ti = 1 week and in the time X2 = 12 weeks after the dissolution. In the parentheses, the interval showing the confidence range of the analysis is given.
Content of NBPT [Wt. %]
Solvent
0 weeks 1 week 12 weeks
MDPG 20.63 (20.34 - 20 92) 19.91 (19.75 - 20.07) 20.4 (20.02-20 .75)
MDGE 21.03 (21.00 - 21 .06 19.97 (19.68 - 20.26) 20.6 (20.50-20 .66)
MTGE 21.72 (21.62 - 21 82) 20.57 (20.27 - 20.87) 21.1 (20.82-21 .36)
The results show that the solvent systems of the present invention have a stabilizing effect towards NBPT, even at the water content of 1 wt. %. After twelve weeks of storage, no evidential decrease of the content of the active component NBPT occurred in any sample (the method used can determine the change at least 1 wt. %).
Industrial applicability
The solutions of N-alkyl thiophosphoric acid triamides in the solvent systems of the present invention can be long-term stored, used for the impregnation of solid urea- containing fertilizers, such as e.g. granular urea, added into the mixture for the manufacture of solid urea-containing fertilizers or added into liquid urea-containing fertilizers.

Claims

C L A I M S
1. A solvent system for the preparation of N-alkyl thiophosphoric triamide solutions, characterized in that it contains one or more glycol ethers of the general formula I
wherein R1 is hydrogen or methyl, R2 is selected from the group consisting of CrC6 alkyl, C3-C6 isoalkyl, C4-C6 tertiary alkyl, n = 2-4, and optionally further auxiliary substances improving the stability and applicability properties of the solutions.
2. The solvent system according to claim 1 , characterized in that the glycol ethers are selected from the group comprising diethyleneglycol monomethylether, dipropyleneglycol monomethylether, triethyleneglycol monomethylether and diethyleneglycol monobutylether.
3. The solvent system according to claim 2, characterized in that the glycol ether is diethyleneglycol monomethylether.
4. The solvent system according to any of claims 1 to 3, characterized in that it contains crystallization inhibitors, surface active agents or colouring agents as the auxiliary substances.
5. The solvent system according to claim 4, characterized in that it contains polyvinylpyrrolidone or N-methylpyrrolidone as the crystallization inhibitors.
6. The solvent system according to claim 5, characterized in that it contains polyvinylpyrrolidone in the concentration range of from 0.01 to 5 wt. % as the crystallization inhibitor.
7. A composition containing N-alkyl thiophosphoric triamide, characterized in that it contains at least one N-alkyl thiophosphoric triamide and the solvent system according to any of claims 1 to 6.
8. The composition according to claim 7, characterized in that the N-alkyl thiophosphoric triamide is N-(n-butyl) thiophosphoric triamide.
9. The composition according to claim 8, characterized in that it contains 1 to 50 wt. % of N-(n-butyl) thiophosphoric triamide.
10. The composition according to claim 9, characterized in that it contains 10 to 40 wt. % of N-(n-butyl) thiophosphoric triamide.
11. The composition according to claim 10, characterized in that it contains 20 to 30 wt. % of N-(n-butyl) thiophosphoric triamide.
12. Use of the composition containing N-alkyl thiophosphoric triamide according to any of claims 7 to 11 as an urease inhibitor in urea-containing fertilizers.
13. The use according to claim 12, wherein the urea-containing fertilizer is solid.
14. The use according to claim 13, wherein the solid urea-containing fertilizer is granular.
15. The use according to claim 12, wherein the urea-containing fertilizer is liquid.
EP07721836A 2006-06-28 2007-06-07 Solvent system for the preparation of n-alkyl thiophosphoric triamide solutions, composition containing n-alkyl thiophosphoric triamide and the use thereof Active EP2032589B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL07721836T PL2032589T3 (en) 2006-06-28 2007-06-07 Solvent system for the preparation of n-alkyl thiophosphoric triamide solutions, composition containing n-alkyl thiophosphoric triamide and the use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZ20060422A CZ301509B6 (en) 2006-06-28 2006-06-28 Solvent system for preparing solutions of thiophosphoric acid N-alkyl triamides, compositions containing thiophosphoric acid N-alkyl triamides and use thereof
PCT/CZ2007/000047 WO2008000196A1 (en) 2006-06-28 2007-06-07 Solvent system for the preparation of n-alkyl thiophosphoric triamide solutions, composition containing n-alkyl thiophosphoric triamide and the use thereof

Publications (2)

Publication Number Publication Date
EP2032589A1 true EP2032589A1 (en) 2009-03-11
EP2032589B1 EP2032589B1 (en) 2011-09-28

Family

ID=38548488

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07721836A Active EP2032589B1 (en) 2006-06-28 2007-06-07 Solvent system for the preparation of n-alkyl thiophosphoric triamide solutions, composition containing n-alkyl thiophosphoric triamide and the use thereof

Country Status (13)

Country Link
EP (1) EP2032589B1 (en)
CN (1) CN101479282B (en)
AT (1) ATE526335T1 (en)
AU (1) AU2007264228B2 (en)
BR (1) BRPI0713788B1 (en)
CZ (1) CZ301509B6 (en)
DK (1) DK2032589T3 (en)
EA (1) EA014854B1 (en)
ES (1) ES2373991T3 (en)
NZ (1) NZ573326A (en)
PL (1) PL2032589T3 (en)
PT (1) PT2032589E (en)
WO (1) WO2008000196A1 (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017019528A1 (en) 2015-07-24 2017-02-02 Koch Agronomic Services, Llc Composition containing n-(n-butyl) thiophosphoric triamide adducts and reaction products
WO2017083714A1 (en) 2015-11-11 2017-05-18 Koch Agronomic Services, Llc Composition containing n-(n-butyl) thiophosphoric triamide adducts and reaction products
WO2018134788A1 (en) 2017-01-20 2018-07-26 Koch Agronomic Services, Llc Composition containing n-(n-butyl) thiophosphoric triamide adducts and reaction products
WO2018134765A1 (en) 2017-01-20 2018-07-26 Koch Agronomic Services, Llc Acid-resistant urease inhibitor adduct -containing fertilizer compositions
WO2018134752A1 (en) 2017-01-19 2018-07-26 Koch Agronomic Services, Llc Enhanced stability of urease inhibitor-containing compositions
US10435333B2 (en) 2015-08-17 2019-10-08 Rhodia Operations High temperature amine-stabilized DCD and/or alkyl thiophosphoric triamide solvent systems and use in agricultural applications
WO2020016830A1 (en) 2018-07-19 2020-01-23 Koch Agronomic Services, Llc Low temperature stable formulations of urease inhibitor-containing compositions
EP3725756A2 (en) 2019-04-18 2020-10-21 Basf Se Compositions with improved urease-inhibiting effect comprising amines, or colorants, and an adduct of the three compounds n-(n-butyl) thiophosphoric acid triamide (nbpt), urea, and formaldehyde
EP3725755A2 (en) 2019-04-18 2020-10-21 Basf Se Compositions with improved urease-inhibiting effect comprising aromatic alcohols, or amines, or amides, and an adduct of the three compounds n-(n-butyl) thiophosphoric acid triamide (nbpt), urea, and formaldehyde
US11053170B2 (en) * 2016-02-24 2021-07-06 Yara International Asa Liquid urease inhibitor formulations
WO2022234504A1 (en) 2021-05-06 2022-11-10 Akcinė bendrovė "ACHEMA" Preparation used as urease inhibitor and urea fertiliser

Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ2008842A3 (en) * 2008-12-23 2010-06-30 Agra Group, A. S. Liquid composition ontaining derivative of phosphoric or thiophosphoric acid thiamide and use thereof
US20100206031A1 (en) 2009-02-17 2010-08-19 Whitehurst Associates, Inc. Amino alcohol solutions of N-(n-butyl)thiophosphoric triamide (NBPT) and urea fertilizers using such solutions as urease inhibitors
US8048189B2 (en) 2009-02-17 2011-11-01 Whitehurst Associates Inc. Buffered amino alcohol solutions of N-(n-butyl)thiophosphoric triamide (NBPT) and urea fertilizers using such solutions as urease inhibitors
BR112014014603B1 (en) * 2011-12-12 2021-06-22 Midtech R&D, Inc. TRIAMIDE N-ALKYL THIOPHOSPHORIC COMPOSITIONS AND METHOD FOR PREPARING AN AGRICULTURAL COMPOSITION
US10173935B2 (en) 2011-12-12 2019-01-08 Rhodia Operations Solvent systems of N-alkyl thiophosphoric triamides and methods of use in agricultural applications
DK2885261T3 (en) 2012-08-15 2019-08-12 Koch Agronomic Services Llc LIQUID COMPOSITIONS CONTAINING UREASE INHIBITORS AND GLYCOLIC COOLETHERS
US9682894B2 (en) 2012-08-15 2017-06-20 Koch Agronomic Services, Llc Compositions of urea formaldehyde particles and methods of making thereof
EP2885263A4 (en) * 2012-08-15 2016-07-06 Koch Agronomic Services Llc Improved compositions of substantially spherical particles
BR112015003095A2 (en) 2012-08-15 2017-07-04 Koch Agronomic Services Llc liquid compositions containing urease and aryl alkyl alcohol inhibitors
AU2013325242B2 (en) 2012-10-01 2018-08-02 Gary David Mcknight Improved liquid formulations of urease inhibitors for fertilizers
KR102022749B1 (en) * 2012-12-20 2019-09-18 로디아 오퍼레이션스 Liquid dicyandiamide and/or alkyl thiophosphoric triamide compositions and their use in agricultural applications
DE102013012760B4 (en) 2013-03-27 2023-07-06 Dreiturm GmbH Compositions containing a dispersed urease inhibitor and their use for the treatment of urea-based fertilizers
ES2529363B1 (en) * 2013-06-06 2016-01-18 Universidad Pública de Navarra Urease inhibitors capable of decreasing nitrate content in vegetables
US8888886B1 (en) 2013-08-06 2014-11-18 Garnett B Whitehurst NBPT solutions for preparing urease inhibited urea fertilizers prepared from N-substituted morpholines
CA2958822A1 (en) 2013-08-23 2015-02-26 Koch Agronomic Services, Llc Urea and nitrogen stabilizer compositions and methods and systems of making and using thereof
CA2931450C (en) 2013-11-26 2020-04-14 Gary David Mcknight Nitrification inhibitors designed for urea and manure based fertilizers
DE202014003261U1 (en) 2014-04-16 2014-05-21 Skw Stickstoffwerke Piesteritz Gmbh Liquid compositions containing a urease inhibitor, and their use for the treatment of urea-based fertilizers
US9650306B2 (en) 2014-04-17 2017-05-16 Gary David McKnight Compositions and methods comprising nitrification inhibitors containing a mixture of protic and aprotic solvent systems
EP3137435A1 (en) 2014-05-02 2017-03-08 Mcknight, Gary, David Increased longevity of nitrogen content of soil through improved liquid delivery formulations of nitrification inhibitors to fertilizers
CN104045465B (en) * 2014-07-04 2016-04-06 上海艾拜克国际贸易有限公司 A kind of solution system and application thereof containing normal-butyl thiophosphoryl triamine
WO2016064973A1 (en) 2014-10-21 2016-04-28 Rhodia Operations Improved solvent systems for dicyandiamide and/or alkyl thiophosphoric triamide and use in agricultural applications
US10501383B2 (en) 2014-10-31 2019-12-10 Koch Agronomic Services, Llc Nitrification inhibitor compositions and methods of making thereof
RU2714723C2 (en) 2014-12-23 2020-02-19 Басф Се Compositions with improved effect of urease inhibition, which contain triamide (thio)phosphoric acid and additional compounds, such as amines and dyes
RU2705277C2 (en) * 2014-12-31 2019-11-06 ДАУ АГРОСАЙЕНСИЗ ЭлЭлСи Nitrification inhibitor compositions and methods for production thereof
AU2016223099B2 (en) 2015-02-24 2019-11-21 Koch Agronomic Services, Llc Granular urea fertilizer with nitrogen stabilizer additives
US10464858B2 (en) * 2015-05-13 2019-11-05 World Source Enterprises, Llc Non-aqueous organo liquid delivery systems containing dispersed poly (organic acids) that improve availability of macro and micro-nutrients to plants
CA2992028C (en) 2015-07-13 2018-11-20 Koch Agronomic Services, Llc Highly concentrated phosphoric or thiophosphoric triamide formulation
CN108026120B (en) * 2015-10-01 2021-11-16 巴斯夫欧洲公司 Process for recovering a mixture containing a (thio) phosphoric acid derivative
WO2017070048A1 (en) 2015-10-19 2017-04-27 Dow Global Technologies Llc Low voc and low odor aromatic oil
EP3585759B1 (en) 2017-02-24 2022-01-12 Yara International ASA Liquid urease inhibitor formulations
US11866383B1 (en) 2018-04-04 2024-01-09 Synsus Private Label Partners, Llc Nitrification inhibiting compositions and their use in agricultural applications
US11124462B1 (en) 2018-08-27 2021-09-21 Hocking International Laboratories, LLC Compositions and their use in agricultural applications
BR112021007333A2 (en) 2018-10-18 2021-07-20 Bayer Aktiengesellschaft heteroarylaminoquinolines and analogues
CN113473860A (en) 2018-12-21 2021-10-01 拜耳公司 1, 3, 4-oxadiazoles and derivatives thereof as novel antifungal agents
BR112022020774A2 (en) 2020-04-16 2022-11-29 Bayer Ag COMBINATIONS OF ACTIVE COMPOUNDS AND FUNGICIDIAL COMPOSITIONS COMPRISING THEM
EP3922619A1 (en) 2020-06-10 2021-12-15 Sasol Chemicals GmbH A solvent composition for a urease inhibitor
DE102021108187A1 (en) 2021-03-31 2022-10-06 Skw Stickstoffwerke Piesteritz Gmbh Granulated pH neutral urea ammonium sulphate fertilizer with urease inhibitor
EP4295688A1 (en) 2022-09-28 2023-12-27 Bayer Aktiengesellschaft Active compound combination

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4530714A (en) * 1983-03-16 1985-07-23 Allied Corporation N-aliphatic and N,N-aliphatic phosphoric triamide urease inhibitors and urease inhibited urea based fertilizer compositions
US5698003A (en) * 1995-12-19 1997-12-16 Imc-Agrico Company Formulation for fertilizer additive concentrate
US20050192319A1 (en) * 1996-09-19 2005-09-01 Albert Boeckh Spot-on formulations for combating parasites

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008000196A1 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017019528A1 (en) 2015-07-24 2017-02-02 Koch Agronomic Services, Llc Composition containing n-(n-butyl) thiophosphoric triamide adducts and reaction products
US10435333B2 (en) 2015-08-17 2019-10-08 Rhodia Operations High temperature amine-stabilized DCD and/or alkyl thiophosphoric triamide solvent systems and use in agricultural applications
WO2017083714A1 (en) 2015-11-11 2017-05-18 Koch Agronomic Services, Llc Composition containing n-(n-butyl) thiophosphoric triamide adducts and reaction products
US11053170B2 (en) * 2016-02-24 2021-07-06 Yara International Asa Liquid urease inhibitor formulations
WO2018134752A1 (en) 2017-01-19 2018-07-26 Koch Agronomic Services, Llc Enhanced stability of urease inhibitor-containing compositions
WO2018134788A1 (en) 2017-01-20 2018-07-26 Koch Agronomic Services, Llc Composition containing n-(n-butyl) thiophosphoric triamide adducts and reaction products
WO2018134765A1 (en) 2017-01-20 2018-07-26 Koch Agronomic Services, Llc Acid-resistant urease inhibitor adduct -containing fertilizer compositions
WO2020016830A1 (en) 2018-07-19 2020-01-23 Koch Agronomic Services, Llc Low temperature stable formulations of urease inhibitor-containing compositions
EP3725756A2 (en) 2019-04-18 2020-10-21 Basf Se Compositions with improved urease-inhibiting effect comprising amines, or colorants, and an adduct of the three compounds n-(n-butyl) thiophosphoric acid triamide (nbpt), urea, and formaldehyde
EP3725755A2 (en) 2019-04-18 2020-10-21 Basf Se Compositions with improved urease-inhibiting effect comprising aromatic alcohols, or amines, or amides, and an adduct of the three compounds n-(n-butyl) thiophosphoric acid triamide (nbpt), urea, and formaldehyde
WO2022234504A1 (en) 2021-05-06 2022-11-10 Akcinė bendrovė "ACHEMA" Preparation used as urease inhibitor and urea fertiliser

Also Published As

Publication number Publication date
EA014854B1 (en) 2011-02-28
DK2032589T3 (en) 2012-01-09
ES2373991T3 (en) 2012-02-10
CZ301509B6 (en) 2010-03-31
PT2032589E (en) 2012-01-11
PL2032589T3 (en) 2012-02-29
CN101479282B (en) 2012-01-18
BRPI0713788A2 (en) 2012-10-30
AU2007264228B2 (en) 2012-03-01
BRPI0713788B1 (en) 2023-03-14
CN101479282A (en) 2009-07-08
WO2008000196A1 (en) 2008-01-03
ATE526335T1 (en) 2011-10-15
EP2032589B1 (en) 2011-09-28
NZ573326A (en) 2010-09-30
EA200802353A1 (en) 2009-04-28
AU2007264228A1 (en) 2008-01-03

Similar Documents

Publication Publication Date Title
EP2032589B1 (en) Solvent system for the preparation of n-alkyl thiophosphoric triamide solutions, composition containing n-alkyl thiophosphoric triamide and the use thereof
EP2376506B1 (en) Liquid composition containing phosphoric or thiophosphoric triamide derivative and use thereof
EP2885261B1 (en) Liquid compositions containing urease inhibitors and glycol alkyl ethers
US9212101B2 (en) Liquid compositions containing urease inhibitors and aryl alkyl alcohols and methods of making and use thereof
CN107207375B (en) Solvent for thiophosphoric triamide or dicyandiamide solutions, and related methods
US10487019B2 (en) Highly concentrated phosphoric or thiophosphoric triamide formulation
CN108026119B (en) Low VOC and low odor perfume oils
CA3177845A1 (en) A solvent composition for a urease inhibitor, application and use thereof

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20081203

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

17Q First examination report despatched

Effective date: 20090730

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

DAX Request for extension of the european patent (deleted)
GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602007017511

Country of ref document: DE

Effective date: 20111201

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: R. A. EGLI & CO. PATENTANWAELTE

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20111226

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110928

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110928

REG Reference to a national code

Ref country code: SK

Ref legal event code: T3

Ref document number: E 10550

Country of ref document: SK

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2373991

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20120210

REG Reference to a national code

Ref country code: EE

Ref legal event code: FG4A

Ref document number: E006153

Country of ref document: EE

Effective date: 20111202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110928

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110928

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20110402970

Country of ref document: GR

Effective date: 20120206

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110928

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120128

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110928

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E013347

Country of ref document: HU

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20120629

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602007017511

Country of ref document: DE

Effective date: 20120629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110928

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120607

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

REG Reference to a national code

Ref country code: EE

Ref legal event code: HC1A

Ref document number: E006153

Country of ref document: EE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20230703

Year of fee payment: 17

Ref country code: CH

Payment date: 20230702

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IE

Payment date: 20240618

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20240618

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LT

Payment date: 20240520

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240612

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20240619

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20240627

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20240617

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20240618

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SK

Payment date: 20240513

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20240618

Year of fee payment: 18

Ref country code: EE

Payment date: 20240619

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20240508

Year of fee payment: 18

Ref country code: PT

Payment date: 20240522

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20240510

Year of fee payment: 18

Ref country code: LV

Payment date: 20240619

Year of fee payment: 18

Ref country code: HU

Payment date: 20240510

Year of fee payment: 18

Ref country code: BE

Payment date: 20240617

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20240530

Year of fee payment: 18